Recent Developments in Coating Technologies for Adsorption Heat Pumps: A Review
Abstract
:1. Introduction
2. Adsorbent Coating Technologies
2.1. Consolidated Beds
2.2. In Situ Direct Synthesis
2.3. Binder-Based Coatings
- The dip-coating technique (Figure 6a) is suitable for the production of uniform thickness coatings. The substrate is fully immersed into the composite coating solution, extracted and then dried. This technique requires the high consumption of solution which sometimes makes it economically unaffordable. Moreover, some limits can be represented by the need for constant control of the viscosity of the solution and of immersion/extraction speed. It is suitable for complex geometries but not for thicknesses that are too high because it may require many deposition steps. Furthermore, it often requires a pre-treatment step in order to increase the interfacial adhesion of the coating to the metal substrate.
- Spray coating (Figure 6b), like dip coating, is suitable for complex heat exchange geometries. It requires a lower consumption of solution and is less affected by, but not exempt from, the viscosity concerns observed in the dip-coating process. However, this technique has some issues due to the depth of the flow inside the HEX cavities. Adsorbent materials tend to be deposited mainly on the external surfaces, becoming scarce and not well distributed inside them, leading to an irregular and homogenous coating deposition. However, this technique represents an easy manufacturing technique that could be affordably automated.
- Spin coating (Figure 6c) is a rather cheap and reproducible coating method, but is unsuitable for complex geometries. It can be essentially used on flat surfaces on which it can produce homogeneous coatings, but with a high quantity of waste. A small quantity of coating precursor slurry is applied on the center of a flat substrate and then distributed through the spinner by centrifugal force.
- The “drop-coating” technique (Figure 6d) can be imagined as an evolution of dip-coating, in which the exchanger can be coated by crossing over a liquid solution cascade, followed by single or multiple drying steps. This method has the advantage of being able to be applied on complex surfaces, but requires, as in the dip-coating process, well-defined viscosity control. The main advantage of the process is the low wastage of materials, considering that the solution can be easy collected and re-used. Furthermore, a continuous production of coated adsorber can be applied.
3. Coating Technique Performance Comparison
4. Conclusions and Future Perspectives
Funding
Conflicts of Interest
Abbreviations
AC | activated carbon |
Cp | specific heat (kJ/kg 1C) |
COP | coefficient of performance |
∆Ha | heat of adsorption (kJ/kg adsorbate) |
∆Hv | heat of vaporization (kJ/kg adsorbate) |
m | mass of dry adsorbent (kg) |
mbed | mass of structure of adsorbent bed (kg) |
P | pressure (kPa) |
Q | heat transferred (kJ) |
Qab | heat of isosteric heating process (kJ) |
Qbc | heat of isobaric desorption process (kJ) |
Qcd | heat of isosteric cooling process (kJ) |
Qda | heat of isobaric adsorption process (kJ) |
Ad-HEx | adsorbent e heat exchanger unit |
SCP | specific cooling power (W/kg) |
SHP | specific heating power (W/kg) |
T | temperature (K) |
X | mass fraction of adsorbed adsorbate per dry adsorbent (kg adsorbate/kg dry adsorbent) |
PTFE | polytetrafluoroethylene |
PVA/PVOH | polyvinyl alcohol |
PVP | polyvinylpyrrolidone |
EG | expanded graphite |
PANI | polyaniline |
TCR | thermal contact resistance |
TC | thermal conductivity |
TG | thermogravimetry |
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Ref. | Working Pairs | Binder/Additives | Performed Characterizations | Results |
---|---|---|---|---|
[41] | Silica gel/water | Expanded graphite | Morphology: SEM Adsorption equilibrium: isobars Gas permeability, µ Effective thermal conductivity, λeff | Adsorption: up to 0.32 g/g at 30 °C and 4.3 kPa µ: 18–32 × 10−12 m2 at 8 MPa of compression λeff: 10–18 W/(m K) |
[43] | Activated carbon (AC)/ammonia | Expanded graphite | Morphology: SEM Adsorption equilibrium: isobars Gas permeability, µ Effective thermal conductivity, λeff | Adsorption: up to 0.5 g/g at 50 °C and 2114 kPa µ: 1.0–7.8 × 10−10 m2 with 71% of AC inside the consolidate λeff: 10–18 W/(m K) |
[44] | Zeolite/water | Polytetrafluoroethylene | Thermal conductivity, λ | λ: up to 0.38 W/(m K) |
[21] | Activated carbon/methanol | Polytetrafluoroethylene | Thermal conductivity, λ | λ: up to 0.18 W/(m K) |
[38] | Activated carbon/ethanol | Expanded graphite and Poly(vinyl alcohol) | Adsorption equilibrium: isobars Thermal conductivity, λ | Adsorption up to 0.87 g/g at 20 °C and 4.28 kPa λ: up to 0.72 W/(m K) |
[36] | Silica gel–CaCl2/water | Expanded graphite or copper powders and Polyvinylpyrrolidone | Morphology: SEM Adsorption equilibrium: isotherms Cycling stability Thermal conductivity, λ | Adsorption up to 0.32 g/g at 34.7 °C and 2.5 kPa Stability checked up to 300 cycles λ: up to 0.78 W/(m K) |
[35] | Zeolite 13X/water | Polyaniline | Adsorption equilibrium: isotherms Thermal conductivity, λ | Adsorption up to 0.30 g/g at 30 °C and 2.5 kPa λ: up to 0.78 W/(m K) |
[28] | Silica gel–CaCl2/water | Bentonite | Small-scale prototype testing | COP: 0.15–0.30 Specific cooling power: 150–200 W/kg Global heat transfer coefficient: 80 W/(m2 K) |
Ref. | Working Pairs | Substrate | Performed Characterizations | Results |
---|---|---|---|---|
[52] | SAPO-34/water | Aluminum fibers onto aluminum HEX | Adsorption kinetic on small-scale adsorber Adsorption kinetic on full-scale adsorber | Volumetric-Specific Cooling Power per adsorber (VSCP): 55 kW/m3 (small-scale)–59 kW/m3 (full-scale) Mass-Specific Cooling Power per adsorbent mass (MSCP): 0.96 kW/kg (small-scale)–0.77 kW/kg (full-scale) |
[47] | Zeolite A/water Zeolite X/water | Stainless steel plates | XRD SEM thermal gravimetric analysis (TGA) | Pure adsorbent coating the stainless steel surface Polymeric coating improves the stability of the crystallized layer |
[62] | Zeolite A/water Zeolite X/water | Stainless steel plates | XRD Adsorption kinetic on small-scale adsorber | Pure adsorbent coating the stainless steel surface Mass-Specific Cooling Power per adsorbent mass (MSCP): 5.5 kW/kg (zeolite X) * |
[49] | Zeolite X/water | Stainless steel plates | XRD Adsorption equilibrium: isotherm | Pure adsorbent coating the stainless steel surface Adsorption: up to 0.35 g/g at 40 °C and 0.85 p/p0 |
[50] | Zeolite Y/water | Stainless steel plates | SEM XRD Adhesion DC polarization curves | Good morphology and pure adsorbent coating the stainless steel surface Highest achievable adhesion quality Good protection against corrosion issues |
[19] | Zeolite A/water | Copper and stainless steel fibrous plates | XRD 3D laser microscope Adsorption kinetic on small-scale adsorber | Pure adsorbent coating the surfaces Good distribution of the coating over the fibers Mass-Specific Cooling Power per adsorbent mass (MSCP): 4-6 kW/kg (varying with substrate) * |
[26] | Metal–organic framework-MOF (aluminum fumarate)/water | Aluminum sheet | XRD Optical microscope and SEM Adsorption equilibrium: isobar Thermal conductivity, λ | Pure adsorbent coating the surfaces Coating uniform and with a microporous structure Adsorption: up to 0.35 g/g at 40 °C and 5.6 kPa λ: 0.3 W/(m K) |
[55] | MOF (HKUST)/water | Copper sheet | XRD Optical microscope and SEM FT-IR Thermal conductivity, λ | Pure adsorbent coating the surfaces λ: 1.4 W/(m K) |
[60] | SAPO34/water | Graphitic supports | XRD SEM Adsorption equilibrium: isobar | Pure adsorbent coating the surfaces Coating well-distributed and adherent on the surface Adsorption: up to 0.25 g/g at 40 °C and 2.5 kPa |
Ref. | Working Pairs | Binder Type and Amount | Substrate | Performed Characterizations | Results |
---|---|---|---|---|---|
[18] | SAPO-34/water | Silane-10 wt.% | Aluminum finned flat-tube HEX | Mechanical characterization Adsorption kinetic small-scale Lab-scale adsorber testing | Pull-off strength: 0.63 MPa; peel detached area: 21.0% (3B index); Damage impact energy: 177.7 mJ; microhardness: 2.5 HV; Effective diffusion coefficient: from 1.97 × 10−10 to 1.70 × 10−11 m2/s Specific Cooling Power: 675 W/kgads Volumetric Cooling Power: 93 W/dm3 Cooling COP: 0.24 |
[64] | SAPO-34/water | Bentonite and carbon fibers-20 wt.% | Aluminum plate | XRD Adsorption equilibrium: isobars Large Pressure Jump kinetic | Crystalline structure confirmed after the synthesis Adsorption up to 0.235 g/g at 30 °C and 1.2 kPa Effective diffusion coefficient: from 1 × 10−3 to 3.5 × 10−3 m2/s Effective thermal conductivity: up to 0.8 W/(m K) |
[65] | AlPO-18/water | Polyvinyl alcohol (PVOH)—10 wt.% | Aluminum plate | SEM Large Pressure Jump kinetic | Clear macroporosity of the coating highlighted. Good distribution of the binder and powders. Fast kinetic: 90% of conversion in less than 2 min for coating thickness < 200 µm |
[20] | SAPO-34/water FAPO-34/water | Trimethoxypropylsilane—5 wt.% | Aluminum sheet | Nitrogen physisorption SEM Adsorption equilibrium: isotherms Adsorption kinetic | Slight pore volume reduction due to the binder More homogeneous surface for FAPO coating than SAPO one Adsorption kinetic two to three times faster than the same configuration using silica gel as adsorbent SAPO-34 Adsorption up to 0.3 g/g at 20 °C and 0.7 p/p0 FAPO-34 Adsorption up to 0.24 g/g at 20 °C and 0.75 p/p0 |
[70] | Zeolite Y/water | Different commercial binders and compositions | Aluminum sheet | Nitrogen physisorption Mechanical stability Thermogravimetric analysis (TGA) Temperature-controlled Diffuse Reflectance Infrared Fourier Transform Spectroscopy (T-DRIFTS) | Reduction in pore volume and specific surface area in line with the binder content Crosscut, bend and impact tests performed to evaluate the most performing coating composition Identification of critical solvent losses for binders having curing process at ambient conditions Loss of absorbance for some of the samples at increasing temperature due to the formation of links |
[71] | SAPO-34/water Zeolite Y/water | Commercial silicone resin—from 3 to 25 wt.% | Aluminum plate | Coating thickness Cycling stability Adsorption equilibrium: isobars Large Pressure Jump kinetic | Average thickness 240 µm for SAPO-34 with 25 wt.% of binder Coating almost destroyed after 500 hydrothermal cycles with 2.5 wt.% of binder. Stable, with color variation, up to 3000 cycles for the one with 25 wt.% of binder. Adsorption capacity reduction in line with the amount of binder. Fast adsorption kinetic independently on the amount of binder. |
[72] | AQSOA Z02 (commercial SAPO-34)/water | Unknown (commercial product) | Aluminum plate and finned-tube HEX | Large Temperature Jump kinetic Single module testing | Small scale kinetic two times faster for 200 µm thick coating against 500 µm. Coating of 300 µm 1.8 to 3.8 times faster than loose grains configuration. Thermal COP: 1.25 for 500 µm thick coating; 1.17 for 200 µm thick coating. |
[73] | SAPO-34/water | Silane—15 wt.% | Graphite plates | Adsorption equilibrium: isobars | Adsorption up to 0.225 g/g at 30 °C and 1 kPa |
[74] | AQSOA Z02 (commercial SAPO-34)/water | Hydroxyethyl ether—5 wt.% | Aluminum sheet | SEM Adsorption equilibrium: isobars Impedance and sorption kinetic | Uniform thickness of the coating Adsorption up to 0.3 g/g at 30 °C and 1.6 kPa Mass transfer identified as main limiting factor during the adsorption regardless the coating thickness |
[66] | Silica gel/water | Polyvinyl alcohol (PVA)—n.a. | Stainless steel tube | Nitrogen physisorption Breakthrough curve | Slight reduction in pore volume and specific surface area due to the binder Thinner layer with larger grain size shows the best performance in terms of mass transfer resistance |
[67] | Silica gel/water | Polyvinylpyrrolidone (PVP)—n.a. | Copper plate | SEM Thermal conductivity, λ | Well distributed silica gel grains inside the coating λ: 0.25–0.3 W/(m K) Thermal contact resistance: 1.29–3.80 K/W |
[27] | Composite silica gel-LiCl/water | Liquid glue—n.a. | Aluminum glue | Nitrogen physisorption Thermal conductivity Sorption kinetic Adsorption equilibrium: isotherms | Pore volume and specific surface area reduction mainly due to LiCl embedding inside the pores λ: 3.3–5.8 W/(m K) Comparable kinetic curve in the first adsorption phase, regardless the salt content, due to the enhanced heat transfer of the coating Adsorption up to 0.65 g/g at 20 °C and 0.8 p/p0 |
[75] | Silica gel/water | Liquid glue—n.a | Finned-tube HEX | Dehumidification performance | Analysis of different operating conditions parameters (e.g., humidity, temperature, heat transfer flow rate etc.) |
[25] | Basolite A520 (commercial aluminum fumarate)/water | Polysiloxane—c.a 23 wt.% | Finned-tube HEX | Lab-scale module testing | Average cooling COP: 0.65 @ 16 °C evaporation temperature Volumetric Specific Cooling Power: 101 W/dm3 |
Reference | Working Pair | Technology | Testing Conditions: Tdes/Tcon/Tads/Tev | Mass SCP (W/kgads) | Volumetric SCP (kW/m3) | COP | Metal-to-Adsorbent Ratio | Coating Thickness (µm) | HEX Volume (dm3) |
---|---|---|---|---|---|---|---|---|---|
[18] | SAPO-34/water | Binder based | 90/28/28/15 °C | 675 | 93 | 0.24 (cooling) | 6.07 | 100 | 1.0 |
[52] | SAPO-34/water | In situ crystallization | 90/21/39.8 °C Pressure jump from 2.6 to 11 mbar | 770 | 59 | - | 5.55 | 45 | 3.0 |
[28] | SWS 1L/water | Consolidated bed | 95/35/20/12 °C | 150-200 | - | 0.15–0.3 (cooling) | 3.47 | - | 8.6 |
[72] | AQSOA 02/water | Binder based | 90/35/35/5 °C | - | - | 1.17–1.25 (heating) | 2.58–4.37 | 300–500 | 15.4 |
[72] | AQSOA 02/water | Binder based | 90/35/35/5 °C | - | - | 1.21–1.23 (heating) | 2.59–2.85 | 150–200 | 1.69 |
[25] | Aluminum fumarate MOF/water | Binder based | 65/35/35/22–10 °C * 90/30/30/18 °C ** | 1394 | 101 | 0.1–0.7 (cooling) | 6.08 | 300–330 | 6.77 |
[78] | AQSOA 01/water | Binder based | 70/34–28/34–28/13–7 °C | 50–350 | - | 0.1–0.4 (cooling) | - | - | - |
[76] | AQSOA 02/water | Binder based | 90/30/30/15 °C | 250–480 | 45–90 | 0.18–0.34 | 3.13 | 330 | 4.08 |
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Caprì, A.; Frazzica, A.; Calabrese, L. Recent Developments in Coating Technologies for Adsorption Heat Pumps: A Review. Coatings 2020, 10, 855. https://doi.org/10.3390/coatings10090855
Caprì A, Frazzica A, Calabrese L. Recent Developments in Coating Technologies for Adsorption Heat Pumps: A Review. Coatings. 2020; 10(9):855. https://doi.org/10.3390/coatings10090855
Chicago/Turabian StyleCaprì, Angela, Andrea Frazzica, and Luigi Calabrese. 2020. "Recent Developments in Coating Technologies for Adsorption Heat Pumps: A Review" Coatings 10, no. 9: 855. https://doi.org/10.3390/coatings10090855